BR0013144B1 - dyed cellulosic molded bodies, a process for their production and the use of a dye containing heavy metals on the basis of titanium or spinel oxide (mgal2o4). - Google Patents

Abstract

The present disclosure relates to novel dyed cellulosic moulded bodies, in particular to fibers or films, containing a heavy-metal-containing colorant, which, according to the thermal stability test described herein, reduces the rise temperature of a cellulose solution in a tertiary amine oxide by 10° C. at most, in particular by 5° C. at most. The moulded bodies according to the disclosure may be produced in accordance with the amine-oxide process.

Description

Report of the Invention Patent for "DYED CELLULOSTIC MOLDED BODIES, PROCESS FOR THE PRODUCTION OF THEME AND USE OF A DYE CONTAINING HEAVY METHYLES OR SPINELIUM (MgAI2O4)".

The invention relates to novel dyed cellulosic molded bodies and a process for producing such molded bodies.

The term "molded bodies" shall mean for the purposes of this disclosure and patent claims, particularly fibers and films. If "fibers" are mentioned below, this means fibers, films and also other molded bodies.

Synthetic fibers, such as polyamide and polyester, as well as viscose fibers, are currently routinely dyed in bulk in spinning. For spinning pretending, only pigments are used, which most often come to the market in the form of pellet marks or pasty products.

In general, pigments are dispersed in the melt or polymer mass. In viscose spinning dyeing, pigment preparations are added either in portions or to the main viscose supply.

The advantages of a spinning dye are, among others:

- Large loads of the same shade can be obtained.

Dyeing has high wet strengths.

- The conventional dyeing process is suppressed, thereby saving energy, saving raw material (chemicals, water) and lower wastewater loading.

- There is no loss of dye.

- The problem of dye braiding (streaking) is suppressed.

- A homogeneous dye distribution is obtained in the fiber and thus a uniform total dyeing.

- In the case of a spinning dosage, rapid shade changes are possible.

As an alternative to the viscose process, a number of processes have been described in recent years in which cellulose is dissolved, without forming a derivative, in an organic solvent, a combination of an organic solvent with an organic salt or in saline solutions. watery. Cellulose fibers, which are produced from these solutions, have been given the generic name Lyocell by BISFA (The International Bureau for the Standardization of Man Made Fibers). By Lyocell is defined by BISFA a cellulose fiber, which is obtained by a spinning process of an organic solvent. By "organic solvent" is meant by BISFA a mixture of a chemical and water.

A known process for producing Lyocell fibers is called the aminoxide process. In this case, a cellulose suspension in an aqueous tertiary aminoxide, preferably N-methylmorpholin-N-oxide (NMMO), is formed by evaporation of excess water, a cellulose solution which is extruded by a spinneret. The formed filaments are guided through an air gap in a precipitated bath, washed and dried. Such a process is described, for example, in US-A-4 246 221.

Due to the advantages in principle of spinning dyeing, the development of spinning dyeing processes for Lyocell fibers was also attempted. In this case, it has been shown that performing a spin dye in the aminoxide process is associated with several problems.

Thus, due to the circulating conduction, in the amino acid process enrichment of pigments, dyes and additives (eg pigment preparations) may occur. Also due to the thermal instability of the cellulose-aminoxide solutions, a very narrow color choice results. In addition, wiring problems arising from agglomerated pigment particles need to be taken into account.

Austrian patent document AT-GM-002 207 U1 teaches that dyes suitable for Lyocell fiber spinning dyeing must be insoluble in the cellulose solution by more than 95% by weight with respect to the dye or dye precursor originally used. , and metal-containing dyes should not be added to the suspension prior to production of the solution, but provided sufficient insolubility can be added to the spinning solution without problems.

Table 1 of AT-GM-002 207 U1 cites Sandorin Blue 2 GLS20 as an unsolvable pigment. This dye contains the copper-weighed metal.

Research by the inventors of the present invention has demonstrated that such pigments, despite sufficient insolubility per se, are not suitable for use in aminoxide due to the reduced thermal stability of the cellulose solution. There is, however, a need to be able to use dyes from the wide variety of dyes containing heavy metals for spinning dyeing in the aminoxide process.

Classic inorganic pigments of the yellow and orange range, which are ecologically dubious, are cadmium sulfide and bleach aromatic. Other pigments are environmentally compatible, such as, for example, natural and synthetic iron oxides, which are widely used in the yellow / red / brown to black color range. However, iron is known to drastically reduce the thermostability of cellulose-aminoxide solutions.

It is known to use titanium dioxide in cellulose fibers. However, unlike the use in paints and varnishes in the painting industry, titanium dioxide is not used as a dye (white pigment) in cellulose fibers, but for maturation, for example, to decrease brightness. One such use of titanium dioxide in the aminoxide process is described in WO-A-96/27638.

The present invention is based on the task of providing dyed cellulosic molded bodies, particularly in the yellow, orange, red and brown color bands which can be produced by spinning dyeing with heavy metal-containing dyes according to the invention. the aminoxide process.

This task is solved according to the invention by the fact that for spinning dyeing a dye is used which, according to the thermostability test described below, reduces the lift temperature of the molding mass or spinning mass, for example. , of the cellulose solution in tertiary aminoxide not more than 10 ° C, in particular not more than 5 ° C. It has been shown that even dyes containing heavy metals can be used in the aminoxide process as long as they meet these criteria.

The dyed cellulosic molded bodies according to the invention contain the heavy metal-containing dye, preferably at 0.20 to 10 wt.%, Particularly at 2.0 to 5.0 wt. cellulose.

Particularly suitable as a dye is one based on titanium or spinel oxide (MgAI2O4), with titanium being partially or magnesium partially or wholly substituted by one or more heavy metal (s).

The invention is further based on the surprising discovery that certain inorganic color pigments from the group of so-called "complex inorganic color pigments" containing heavy metals do not impair the thermostability of the aminoxide cellulose solution and therefore , are very suitable for use in the aminoxide process.

Particularly with these dyes the above described problem of dyeing in the yellow tint can be solved. Based on the known state of the art, it should in fact be assumed that all heavy metals, whose ions have two or more degrees of oxidation, exert a negative effect on the system's thermostability in the aminoxide process. Since this effect on thermostability is catalytic and catalysis - as it is known - may be caused by very small concentrations of active agent, the possibility of using a class of substances containing heavy metals as a dye for dyeing. The wiring in the aminoxide process was totally unexpected.

According to H. Endriss, "Aktuelle anorganische Bunt-Pigmente" (Curt R. Vincentz Verlag, Hannover, 1997), complex inorganic color pigments are divided into two groups:

- Rutile pigments: they are titanium oxides, in which titanium is partially replaced by heavy metals.

- Spinel pigments:

They include numerous compounds of the basic composition, in principle A-B2-O4. Many of these pigments, such as those of type A-Fe2-O4, are not suitable for the amino acid process.

Surprisingly, however, it has been shown that spinel-based pigments (MgAI2O4), in which Mg is partially or fully replaced by chromophoric heavy metals, are very well suited for the aminoxide process. In this case the term "spinel" means, and in general, in connection with the present invention, the spinel mineral, characterized by the chemical formula MgAI2O4.

The heavy metal (s) are conveniently selected from the group consisting of nickel, chromium, manganese, antimony and cobalt and are preferably in oxidized form.

In the case of titanium oxides with heavy metal oxides, they are preferably called rutile pigments. In rutile pigments, the rutile structure of titanium dioxide absorbs nickel (II) oxide or chromium (III) oxide or manganese oxide (II) as a chromophoric component as well as, for example, antimony oxide. (V) or niobium oxide (V), for valence compensation purposes, so that an average valence of four is obtained, as in titanium (F. Hund, Angew. Chemie 74, 23 (1962)).

Preferred embodiments of the dyed cellulosic molded bodies of the invention are therefore characterized by the fact that they contain a dye based on titanium oxide, with the titanium oxide being partially substituted by nickel (II) oxide, oxide chromium (III) or manganese oxide (ll) or antimony oxide (V).

In another preferred embodiment, the cellulosic molded bodies contain a spinel base dye (MgAI 2 O 4), where magnesium is partially or totally substituted by cobalt. Metal oxides, when incorporated into the host structure, lose their original chemical, physical and physiological characteristics. Nickel-titanium yellow is a citrus pigment. Chromium titanium yellow varies in soft to medium ocher color according to drying temperature and particle size. More detailed information on the pigments used according to the invention is contained in H. Endriss, "Aktuelle anorganische Bunt-Pigmente" (see above).

Appropriate pigments of this type are shown below with their color index. These pigments are produced, for example, by the company BASF Aktiengesellschaft, Ludwigshafen, Germany under the trade names listed below:

Pigment Color Index (Cl) | MarcadeBASF Titanium Dioxide Analysis

Yellow Pigment Cl 52/77788 Antimony Nickel Sicotan Gelg K1011

Yellow Pigment Cl 24/77310 Chrome / Antimony Sicotan Gelg K2001 FG

Cldepigmentoamareb 24/77310 chrome / antimony Sbotan Gelg K 2011

Amareb pigment cl 24/77310 chromeZantimonb Sbotan Gelg K 2107

Amareb pigment cl 24/77310 chrome / antimony Sbotan Gelg K 2112

Amareb pigment cl 164/77899 chrome / antimony Sbotan Gelg K 2107

Despite the high heavy metal contents, the aforementioned pigments are toxicologically acceptable. Chromium / nickel / manganese / antimony are biologically inactive in the pigment. Therefore, these pigments are also allowed for use in food packaging.

The dyed cellulosic molded body of the invention is preferably a fiber or film and is preferably produced according to an aminoxide process.

The invention also relates to a process for producing dyed cellulosic molded bodies in which a cellulose solution in an aqueous tertiary aminoxide is molded using a molding tool, particularly a die, and is conducted through a slot. in a precipitated bath to precipitate the dissolved cellulose, and a dye is added to the cellulose solution or a precursor of the cellulose solution and is characterized in that a dye containing heavy metals is added. , which, according to the thermal stability test described below, reduces the elevation temperature of the cellulose solution in tertiary aminoxide by a maximum of 10 ° C, in particular by a maximum of 5 ° C. .

Preferably, in the process according to the invention a dye is added on the basis of titanium or spinel oxide (MgAI 2 O 4), with titanium being partially substituted or more heavy metals and magnesium respectively being partially or totally substituted by one or more metals) heavy.

The invention further relates to the use of a heavy metal-containing dye as a cellulosic molded body dye. Such dye according to the thermostability test described below reduces the elevation temperature of a cellulose solution in an aminoxide. at a maximum of 10 ° C, in particular at a maximum of 5 ° C.

Preferably, titanium or spinel oxide (MgAl2O4) is used as a dye for cellulosic molded bodies, the titanium contained in the titanium oxide being partially substituted by one or more weighted metals and the magnesium contained in the spinel respectively. totally or totally replaced by one or more heavy metals.

The present invention is explained below in further detail by way of examples.

Example 1

Effect of various dyes used according to the invention on NMMO spinning mass thermostability.

A: Cl yellow pigment 53/77788 (Sicotan Gelb K 1011)

B: Cl yellow pigment 24/77310 (Sicotan Gelb K 2011)

C: Cl yellow pigment 164/77899 (Sicotan Braun K 2711)

D: Cl blue pigment 28/77346 (Sicopal Blau K 6310; manufacturer: BASF AG,

Ludwigshafen, Germany); a spinel pigment based on MgAI2O4, in which magnesium is completely replaced by cobalt.

Test Run (thermostability test): The tests were performed with a Sikarex device (Sikarex TSC 512, manufacturer: System-Technik AG, Rüschlikon, Switzerland). In this case, the NMMO wiring mass is thermally requested in Sikarex through a set temperature program until an exothermic reaction (wiring mass disintegration) occurs.

11.5 g pulverized spinning mass, 13.5 wt% cellulose, 75 wt% NMMO and 11.5 wt% water, where 5 wt% of each dye A, B, C or D, for cellulose, were homogenically added, weighed in a glass load into the Sikarex pressure vessel and subjected to a Sikarex isothermal staged experiment. In this case, in the first stage, it was heated to 90 ° C at a heating rate of 60 ° C / h, followed by a stabilization period in which a change to a heating rate of 6 ° C / h was made. H. Then, in a second stage, it was heated to 180 ° C with this heating ratio. The temperature of the spinning mass in Sikarex was also measured.

For comparison purposes, a spinning mass of NMMO E, which was not mixed with dye, was also examined under Sikarex under the same conditions (blank value).

The temperature plots measured for the various wiring masses A - E are shown in Fig. 1, where on the abscissa the temperature T of the heating jacket is given in ° C, while on the ordinate the difference of The temperature ΔΤ between the sample and the heating path is given in ° C.

By the term "lifting temperature" it is understood that the temperature of the heating jacket at which the temperature of the spinning mass due to exothermic reactions exceeds by 100 ° C the temperature of the heating pipe. The dye-free spinning mass (curve E) has an elevation temperature of approximately 165 ° C. The addition of dye A, B, C and D reduced the spinning mass elevation temperature by only approximately 2 ° C.

The results show that the thermostability of a NMMO cellulose spinning mass is not influenced by the addition of, respectively, 5% of each of the dyes used according to the invention. Example 2

The procedure corresponded to that of Example 1, but instead of the dyes used according to the invention, the following other heavy metal containing pigments were used:

F: Bismuth Vanadate - Cl Pigment Yellow 184 (Sicopal Gelb K 1160 FG)

G: Copper-phthalocyanine - Cl pigment blue 15: 3 (Aquarinblue 3 G; manufacturer: Tennants Textile Colors Ltd., Belfast, Northern Ireland.

The results are shown in Fig. 2, where on the abscissa is entered the temperature T of the heating jacket, in ° C, and on the ordinate, the temperature difference ΔΤ between sample and heating jacket, in ° C.

Figure 2 shows that FeG dyes reduce tempera-

increase the wiring mass from 165 ° C (curve E) to 150 ° C (curve F) or 149 ° C (curve G). They reduce the lift temperature by 15 ° C or 16 ° C. The pigments examined thus catalyze, unlike the pigments used according to the invention, the thermal reduction of the spinning mass and are therefore not suitable as dyes in the aminoxide cellulose system. Example 3

The dyes mixed with dye A, B, C or D according to example 1 were spun at 115 ° C for 1.7 dtex fibers. For good spinning performance, lemon yellow fibers (dye A, ocher fibers (dye B), brown fibers (dye C) and blue fibers (dye D) were obtained.

Claims (16)

1. Dyed cellulosic molded body, characterized in that it contains a dye on the basis of titanium or spinel oxide (MgAI2O4) 1 where titanium is partially replaced by one or more heavy metals and magnesium respectively is partially or wholly substituted by one or more heavy metals and, according to the thermostability test described above, the dye reduces the elevation temperature of the cellulosic molding mass by a maximum of 10 ° C. Dyed cellulosic molding body according to Claim 1, characterized in that the dye reduces the raising temperature of the cellulosic molding mass by a maximum of 5 ° C. A dyed cellulosic body according to claim 1 or 2, characterized in that it contains the dye containing heavy metals at 0.20 to 10% by weight, relative to cellulose. A dyed cellulosic body according to claim 3, characterized in that it contains the dye containing heavy metals in 2.0 to 5.0% by weight, relative to cellulose. Tinted cellulosic body according to any one of claims 1 to 4, characterized in that the heavy metal (s) is (are) chosen from the group consisting of nickel, chromium, manganese. , antimony and cobalt. A dyed cellulosic body according to any one of claims 1 to 5, characterized in that the heavy metal (s) is in oxidized form. A dyed cellulosic body according to claim 6, characterized in that it contains a dye based on the titanium oxide, the titanium oxide being partially substituted by nickel (II) oxide and oxide. of antimony (V). A dyed cellulosic body according to claim 6, characterized in that it contains a dye based on titanium oxide, with titanium oxide partially replaced by chromium (III) oxide and oxide. of antimony (V). A dyed cellulosic body according to claim 6, characterized in that it contains a dye based on titanium oxide, the titanium oxide being partially replaced by manganese oxide (ll) and oxide of antimony (V). A dyed cellulosic body according to claim 6, characterized in that it contains a spinel-based dye (MgAI 2 O 4) 1 where magnesium is partially or totally replaced by cobalt. A dyed cellulosic body according to any one of claims 1 to 10, characterized in that it is a fiber or a film. A dyed cellulosic body according to any one of claims 1 to 11, characterized in that it is produced by an aminoxide process. A process for producing dyed cellulosic molded bodies as defined in any one of claims 1 to 12, wherein a cellulose solution in an aqueous tertiary aminoxide is molded using a molding tool, particularly a spinneret, and driven through. of an air gap in a precipitation bath to precipitate the dissolved cellulose, and to the cellulose solution and / or a precursor of the cellulose solution is added a dye, characterized in that a dye containing heavy metals based on titanium or spinel oxide (MgAI2O4) 1 where titanium is partially substituted by one or more heavy metals and magnesium respectively is partially or totally replaced by one or more heavy metals) which, as defined in the thermostability test described above, reduces the elevation temperature of the cellulose solution in tertiary aminoxide by a maximum of 10 ° C. Process for the production of dyed cellulosic molded bodies according to claim 13, characterized in that the dye reduces the elevation temperature of the tertiary amine oxide cellulose by a maximum of 5 ° C. 15. Use of a dye containing heavy metals on the basis of titanium or spinel oxide (MgAI2O ^), characterized in that it is used as a dye for cellulosic molded bodies, with titanium contained in titanium oxide being partially substituted or magnesium contained in the spasmelium, respectively, is partially or wholly replaced by one or more heavy metals, which, as defined in the thermal stability test described above, reduces the elevation temperature of a cellulose solution by one. tertiary aminoxide not more than 10 ° C. Use of a dye according to claim 15, characterized in that it reduces the elevation temperature of a cellulose solution in a tertiary aminoxide by a maximum of 5 ° C.